KR102521281B1 - Hybrid composite comprising metal-organic framework and two-dimensional metal carbide sheet and manufacturing method thereof - Google Patents

Abstract

A hybrid composite comprising a metal-organic framework (MOF) and a two-dimensional metal carbide sheet is disclosed. Since the hybrid composite has high porosity and excellent electrical conductivity, when used in an electrode such as a supercapacitor or a secondary battery, the energy density and output characteristics of the device can be improved.

Description

A hybrid composite comprising a metal-organic skeleton and a two-dimensional metal carbide sheet and a manufacturing method thereof

The present invention is a hybrid composite comprising a metal-organic framework (MOF) and a two-dimensional metal carbide sheet, particularly a cathode or anode material for a battery for mobile IT devices, electric vehicles (EVs), and energy storage devices (ESS), catalysts and It relates to a hybrid composite that can be used as an electromagnetic wave shielding material.

Due to the discovery of more than 20,000 Metal-Organic Frameworks (MOFs) with a vast array of advanced functions, building blocks such as various metal nodes and organic linkers Numerous studies on the synthesis of MOFs have been conducted over the past decades by a rich variety of building blocks. In this regard, the basic synthesis protocol of the MOF is by self-assembly of building blocks such as metal nodes and organic interconnects, and has a relatively simple synthesis method.

On the other hand, in the case of the MOF, it has micropores and mesopores of various sizes and has a very wide specific surface area, so it has been mainly used as a gas storage body. In addition, since the combination of metal precursors and organic ligands included in MOF is very diverse, thousands of crystal structures are registered in the database, and since various functional groups can also be included, it is spotlighted as a promising material in various industrial fields. there is. However, from the electrochemical point of view, its utilization is declining due to the low conductivity of MOF itself, and thus, active research is being conducted to synthesize a MOF having conductivity.

On the other hand, a super-capacitor is a capacitor with a very large capacitance, and is called an ultra-capacitor or ultra-high-capacitance capacitor in Korean. In academic terms, it is called an electrochemical capacitor, distinguishing it from the existing electrostatic or electrolytic capacitor. Supercapacitors, unlike batteries that use chemical reactions, use simple ion movement to the interface between electrodes and electrolytes or charge by surface chemical reactions. Accordingly, it is attracting attention as a next-generation energy storage device that can be used as an auxiliary battery or a battery replacement because of its rapid charge and discharge capability, high charge and discharge efficiency, and semi-permanent cycle life characteristics.

Supercapacitors have been commercialized since the 1980s, and their development history is relatively short, but they have developed through the development of hybrid product design technology that uses asymmetric electrodes and new electrode materials such as metal oxides and conductive polymers that have been traditionally used. The speed is very fast. Recently announced products have energy densities that exceed those of Ni-MH batteries, and in Japan, this rapid development of technology is referred to as the “storage revolution.”

Supercapacitors, which are next-generation energy storage devices, can quickly store, take out, and use large amounts of electricity, have a high output that is 100 times higher than that of secondary batteries, and can be used semi-permanently. do. In other words, supercapacitors are important as renewable energy storage devices such as solar energy, wind power, and hydrogen fuel cells, which are eco-friendly and clean alternative energy that replaces petroleum and does not emit carbon dioxide.

However, in the case of supercapacitors developed so far, carbon-based electrode materials mainly store energy in the electric double layer, so they have relatively high output characteristics, but have a low energy storage capacity, and metal oxide-based supercapacitors using specific surface area and redox reaction at the same time. has the advantage of exhibiting a high capacitance, but has many problems, such as the disadvantage of being difficult to use in mass production due to the high cost of materials. Therefore, in order to improve the energy density and power density of the supercapacitor, it is urgent to develop inexpensive electrodes with high porosity and electrical conductivity.

Accordingly, the inventors of the present invention prepared a hybrid composite in which a plurality of metal-organic frameworks (MOFs) and a plurality of two-dimensional metal carbide sheets were randomly mixed while researching to solve the above problems, which was used as a supercapacitor or When applied as an electrode of a secondary battery, the present invention was completed by confirming that the performance of a supercapacitor or secondary battery could be improved due to the characteristic high porosity and electrical conductivity characteristics of the hybrid composite. On the other hand, the hybrid composite is applied in various fields such as catalysts for water purification, anticancer drugs, immunodeficiency virus treatments, fungal and bacterial infection treatments, malaria treatments, various drug delivery materials, photocatalysts, sensors, and aerospace materials in addition to supercapacitors or secondary batteries. As this is possible, it can be used as a commercially very useful material.

In addition, conventional MOF electrode materials are carbonized at a high temperature of 800 degrees or more to produce metal oxide / carbon materials and used as energy storage materials such as lithium secondary batteries, but the present invention is a MOF material synthesized in a process of less than 150 degrees and a two-dimensional It is possible to provide a manufacturing method at room temperature using an ultrasonic dispersion method with a metal carbide material.

The present invention has been made to solve the above problems, and one embodiment of the present invention provides a hybrid composite including a metal-organic framework (MOF) and a two-dimensional metal carbide sheet.

In addition, another embodiment of the present invention provides a method for preparing the hybrid composite.

In addition, another embodiment of the present invention provides an electrode including the hybrid composite.

In addition, another embodiment of the present invention provides a catalyst comprising the hybrid composite.

In addition, another embodiment of the present invention provides an electromagnetic wave shielding material including the hybrid composite.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned technical problem, and other technical problems not mentioned are clearly understood by those skilled in the art from the description below. It could be.

As a technical means for achieving the above-described technical problem, one aspect of the present invention,

metal-organic frameworks (MOFs); and a two-dimensional metal carbide sheet, wherein the metal-organic framework and the two-dimensional metal carbide sheet are randomly mixed to provide a hybrid composite having a three-dimensional porous structure.

The two-dimensional metal carbide may be a Mxene nanosheet satisfying at least one selected from the group consisting of Formulas 1 to 6 below.

[Formula 1]

(M or M') _n+1 X _n

[Formula 2]

(M or M") ₂ M' _m X _m+1

[Formula 3]

(M' _a M" _b ) _n+1 X _n

[Formula 4]

M' _1.33 (M or M") _c X

[Formula 5]

(M or M") ₄ M' _m X _m+3

[Formula 6]

(M or M') _d+e+1 X _d X' _e

In Formula 1 to Formula 6, M is at least one metal selected from group VIIB, group VIIIB, group IB, group IIB W and Y, and M 'is selected from group IVB, group VB, group VIB and Sc At least one metal, M" is a metal selected from the same group as M' but not the same as M', X and X' include one or more selected from C or N, and X' is X and It is different, n is an integer from 1 to 3, m is selected from 1 or 2, a + b is 1, c is 0 or 0.67, and d + e may be an integer from 1 to 3.

The two-dimensional metal carbide sheet is Ti ₂ C, (Ti _0.5 ,Nb _0.5 ) ₂ C, V ₂ C, Nb ₂ C, Mo ₂ C, Mo ₂ N, (Ti _0.5 ,Nb _0.5 ) ₂ C, Ti ₂ N, W _1.33 C, Nb _1.33 C, Mo _1.33 C, Mo _1.33 Y _0.67 C, Ti ₃ CN, Zr ₃ C _2, Hf ₃ C _2, Ti ₄ N ₃ , Nb ₄ C ₃ , Ta ₄ C ₃ , V ₄ C ₃ , (Mo,V) ₄ C _{3 ,} Mo ₄ VC ₄ Mo ₂ TiC ₂ , Cr ₂ TiC ₂ , Mo ₂ ScC ₂ , Mo ₂ Ti ₂ C ₃ , and Ti ₃ C ₂ selected from the group consisting of It may be characterized in that it is a MXene nanosheet containing one or more types.

The metal-organic framework may have a structure represented by Chemical Formula 7 below.

[Formula 7]

M-L-M

In Formula 7, M is a metal, and L is an organic ligand and may include any one of the structures of Formulas 8 to 12 below.

[Formula 8]

In Formula 8, X1, X2. X4 and X5 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X4 and X5 are the same, X1 and X5 are the same as or different from each other, , X3, and X6 may each independently be hydrogen, an amine group (NH2), a carboxy group (COOH), or a hydroxyl group (OH).

[Formula 9]

In Formula 9, X1 to X10 are each independently hydrogen, an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), and when X1 and X3 are the same, X1 and X2 are the same as each other, and X3 and When X4 is equal to each other, X1 and X3 are different from each other, X1 and X4 are equal to each other, X2 and X3 are equal to each other, and n may be an integer from 0 to 5.

[Formula 10]

In Formula 10, X1 to X6 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), X1 and X2 are the same, X3 and X4 are the same, and X5 and X6 are are the same as each other, X1, X3 and X5 are the same as or different from each other, and Y1 to Y6 may each independently represent carbon or nitrogen.

[Formula 11]

In Formula 11, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are are the same as or different from each other, and R1, R3, R4 and R6 are each independently selected from straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched chain C1-C10 alkyl, Branched C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl, R2 and R5 are each independently an amine group ( NH2), carboxy group (COOH), hydroxyl group (OH), straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched chain C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.

[Formula 12]

In Formula 12, R1 to R4 are each independently hydrogen, straight-chain or branched-chain C1-C10 alkyl, straight-chain or branched-chain C1-C10 alkoxy, straight-chain or branched-chain C1-C10 aminoalkyl, straight or branched chain C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.

M is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re , Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub, and combinations thereof.

The hybrid composite may have a BET specific surface area of 30 m ² /g to 1000 m ² /g.

The metal carbide sheet may have a thickness of 1 to 20 nm and an area of 100 nm ² to 100 μm ² .

The amount of the metal carbide sheet relative to 100 parts by weight of the metal-organic framework may be 20 parts by weight to 70 parts by weight.

The hybrid composite may have a total pore volume of 0.1 cm3/g to 1.0 cm3/g.

Electrical conductivity of the hybrid composite may be greater than or equal to 250 S·m ⁻¹ .

In another aspect of the present invention, mixing the organic ligand and the metal precursor; and mixing a two-dimensional metal carbide sheet with the mixture; It provides a method for preparing the hybrid complex, wherein the substituent included in the organic ligand forms a coordination bond with the metal precursor, respectively.

The metal-organic framework (MOF) obtained by mixing the organic ligand and the metal precursor has a two-dimensional shape, and prior to mixing the two-dimensional metal carbide sheet, the metal-organic framework is ultrasonicated in a solvent. dispersing; may further include.

Prior to the step of mixing the two-dimensional metal carbide sheet, ultrasonically dispersing the two-dimensional metal carbide sheet in a solvent; may further include.

Mixing the two-dimensional metal carbide sheet with the mixture may be performed by ultrasonic dispersion.

The ultrasonic dispersion may be characterized in that it is performed for a time of 30 minutes to 240 minutes or less.

Another aspect of the present invention provides an electrode comprising the hybrid composite.

Another aspect of the present invention provides a catalyst comprising the hybrid composite.

Another aspect of the present invention provides an electromagnetic wave shielding material including the hybrid composite.

According to one embodiment of the present invention, the hybrid composite includes both the characteristic electrical conductivity and porosity of the metal-organic framework (MOF) and the characteristic electrical conductivity and porosity of the metal carbide sheet, and the metal-organic framework ( MOF) and the metal carbide sheet may have a very high porosity because they also include three-dimensional pores generated by randomly mixing. Therefore, since the hybrid composite has high porosity and excellent electrical conductivity, when used in an electrode such as a supercapacitor or a secondary battery, the energy density and output characteristics of the device can be improved.

In addition, since the hybrid composite uses a manufacturing method using an ultrasonic dispersion method in a process of less than 150 degrees, the preparation of the hybrid composite is relatively easy, saves energy, and is therefore environmentally friendly. In addition, since the manufacturing method is simple and mass production is possible, it may be industrially very useful.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a schematic diagram showing a two-dimensional Mxene structure according to an embodiment of the present invention.
2 is a SEM picture of the surface of a metal carbide Ti ₃ C ₂ T _x sheet prepared according to an embodiment of the present invention.
3 is a low-magnification SEM photograph of a metal carbide Ti ₃ C ₂ T _x sheet prepared according to an embodiment of the present invention.
4 is a SEM image of the surface of the metal-organic framework Ni ₃ (HITP) ₂ prepared according to an embodiment of the present invention.
5 is a schematic view of manufacturing a Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x 3-dimensional composite according to an embodiment of the present invention.
6 illustrates a method for manufacturing a Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x composite using an ultrasonic dispersion method and a vacuum filtration process according to an embodiment of the present invention.
7 schematically illustrates a ZIF-8/Ti ₃ C ₂ T _x synthesis manufacturing method according to an embodiment of the present invention.
8 is a SEM image of the surface of the Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x hybrid composite synthesized according to an embodiment of the present invention.
9 is a cross-sectional SEM image of a ZIF-8/Ti ₃ C ₂ T _x composite synthesized according to an embodiment of the present invention.
10 shows a BET N2 adsorption isotherm of Ni ₃ (HITP) ₂ prepared according to an embodiment of the present invention.
11 shows Ti ₃ C ₂ T _x MXene BET N2 adsorption isotherms prepared according to an embodiment of the present invention.
12 shows the BET N2 adsorption isotherm of the ZIF-8/Ti3C2Tx composite prepared according to an embodiment of the present invention.
13 shows N2 adsorption isotherms of the Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x composite prepared according to an embodiment of the present invention.
14 shows Ti ₃ C ₂ T _x MXene BET N2 adsorption isotherms prepared according to an embodiment of the present invention.
15 shows XRD results of each of Ni ₃ (HITP) ₂ , Ti ₃ C ₂ T _x , and Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x samples prepared according to an embodiment of the present invention.
16 is a lithium half-cell for electrochemical evaluation of Ni ₃ (HITP) ₂ , Ti ₃ C ₂ T _x or Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x electrodes prepared according to an embodiment of the present invention. (half-cell) is assembled, and the charge/discharge curve of the initial cycle is shown in the voltage range of 0.0 to 3.0 V (vs. Li ⁺ /Li) at a C-rate of 50 mA/g.

Hereinafter, the present invention will be described in more detail. However, the present invention can be implemented in many different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' a certain element means that other elements may be further included, rather than excluding other elements unless otherwise stated.

The first aspect of the present application is,

metal-organic frameworks (MOFs); and a two-dimensional metal carbide sheet, wherein the metal-organic framework and the two-dimensional metal carbide sheet are randomly mixed to provide a hybrid composite having a three-dimensional porous structure.

Hereinafter, the hybrid composite according to the first aspect of the present application will be described in detail.

In one embodiment of the present application, the hybrid composite includes a metal-organic framework (MOF) and a metal carbide sheet. Therefore, the hybrid composite includes both the unique electrical conductivity characteristics and porosity of the metal-organic framework (MOF) and the metal carbide sheet, and the metal-organic framework (MOF) and the metal carbide Since the sheet also includes three-dimensional pores generated by randomly mixing, it may have a very high porosity.

In one embodiment of the present application, the two-dimensional metal carbide may be characterized in that it is a Mxene nanosheet satisfying at least one selected from the group consisting of Formulas 1 to 6 below.

[Formula 1]

(M or M') _n+1 X _n

[Formula 2]

(M or M") ₂ M' _m X _m+1

[Formula 3]

(M' _a M" _b ) _n+1 X _n

[Formula 4]

M' _1.33 (M or M") _c X

[Formula 5]

(M or M") ₄ M' _m X _m+3

[Formula 6]

(M or M') _d+e+1 X _d X' _e

In Formula 1 to Formula 6, M is at least one metal selected from group VIIB, group VIIIB, group IB, group IIB W and Y, and M 'is selected from group IVB, group VB, group VIB and Sc At least one metal, M" is a metal selected from the same group as M' but not the same as M', X and X' include one or more selected from C or N, and X' is X and are different, n is an integer from 1 to 3, m is selected from 1 or 2, a+b is 1, c is 0 or 0.67, and d+e may be an integer from 1 to 3. Preferably , The two-dimensional metal carbide sheet is Ti ₂ C, (Ti _0.5 ,Nb _0.5 ) ₂ C, V ₂ C, Nb ₂ C, Mo ₂ C, Mo ₂ N, (Ti _0.5 ,Nb _0.5 ) ₂ C, Ti ₂ N, W _1.33 C, Nb _1.33 C, Mo _1.33 C, Mo _1.33 Y _0.67 C, Ti ₃ CN, Zr ₃ C _2, Hf ₃ C _2, Ti ₄ N ₃ , Nb ₄ C ₃ , Ta ₄ C ₃ , selected from the group consisting of V ₄ C ₃ , (Mo,V) ₄ C _{3 ,} Mo ₄ VC ₄ Mo ₂ TiC ₂ , Cr ₂ TiC ₂ , Mo ₂ ScC ₂ , Mo ₂ Ti ₂ C ₃ , and Ti ₃ C ₂ 1 is a schematic diagram of a two-dimensional crystal represented by the chemical formula M _{n + 1} X _n . As shown in the figure, metal It has a structure in which carbon, a non-metal element, is arranged in a lattice structure composed of element M.

In one embodiment of the present application, the mexin structure of the present application may be prepared by removing element A, which is at least one metal selected from the MAX phase structure, selectively, but not limited to, group IIIA, group IVA, and Cd. .

In one embodiment of the present application, the metal-organic framework may have a structure represented by Chemical Formula 7 below.

[Formula 7]

M-L-M

In Formula 7, M is a metal and L is an organic ligand.

Meanwhile, the metal represented by M is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, Lu, Hf , Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub, and combinations thereof. It may be, and may preferably include Ni or Cu. In this regard, depending on the type of metal, the metal-organic framework (MOF) may have semiconducting properties or metalite properties.

In one embodiment of the present application, the organic ligand represented by L in Formula 1 may include any one of the structures of Formulas 8 to 12 below.

[Formula 8]

[Formula 9]

In Formula 9, X1 to X10 are each independently hydrogen, an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), and when X1 and X3 are the same, X1 and X2 are the same as each other, and X3 and When X4 is equal to each other, X1 and X3 are different from each other, X1 and X4 are equal to each other, X2 and X3 are equal to each other, and n may be an integer from 0 to 5.

[Formula 10]

In Formula 10, X1 to X6 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), X1 and X2 are the same, X3 and X4 are the same, and X5 and X6 are are the same as each other, X1, X3 and X5 are the same as or different from each other, and Y1 to Y6 may each independently represent carbon or nitrogen.

[Formula 11]

In Formula 11, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are are the same as or different from each other, and R1, R3, R4 and R6 are each independently selected from straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched chain C1-C10 alkyl, Branched C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl, R2 and R5 are each independently an amine group ( NH2), carboxy group (COOH), hydroxyl group (OH), straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched chain C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.

[Formula 12]

In Formula 12, R1 to R4 are each independently hydrogen, straight-chain or branched-chain C1-C10 alkyl, straight-chain or branched-chain C1-C10 alkoxy, straight-chain or branched-chain C1-C10 aminoalkyl, straight or branched chain C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.

In one embodiment of the present application, the substituent in Chemical Formulas 8 to 12 may preferably be an amine group (NH 2 ), and more preferably may include at least one ortho-diamine group. .

In one embodiment of the present application, the organic ligand may include an aryl core and a substituent (or central element) capable of coordinating with the metal as shown in Chemical Formulas 8 to 12, and the substituent included in the organic ligand is It may be to form a coordinate bond with the metal, respectively. That is, as shown in Chemical Formula 8, the ortho substituents of the organic ligand, X1 to X4 of Chemical Formulas 9 and 11, X1 to X6 of the organic ligand of Chemical Formula 10, and the nitrogen atom included in the ring structure of Chemical Formula 12 coordinate with the metal, respectively. It may be to form a bond. Meanwhile, in the metal-organic framework (MOF), the first organic ligand and the second organic ligand may cross each other to form a coordination bond with the metal. In this case, the metal-organic framework may be one in which the first organic ligand and the second organic ligand form coordination bonds on both sides of one metal, respectively, and have the above structure as a repeating unit to have an extended structure may have

In one embodiment of the present application, preferably, the organic ligand is substituted or unsubstituted benzene-hexamine, substituted or unsubstituted naphthalene-hexamine, substituted or unsubstituted substituted anthracene-hexamine, substituted or unsubstituted tetracene-hexamine, substituted or unsubstituted pentacene-hexamine, substituted or unsubstituted phenanthrene -Hexaamine (phenanthrene-hexamine), substituted or unsubstituted pyrene-hexamine, substituted or unsubstituted chrysene-hexamine, substituted or unsubstituted perylene-hexamine Amine (perylene-hexamine), substituted or unsubstituted fluorene-hexamine, substituted or unsubstituted coronene-hexaamine, substituted or unsubstituted ovalene-hexaamine ( ovalene-hexamine) and the like. More preferably, the organic ligand may be any one selected from compounds 1 to 6 below.

In one embodiment of the present application, the electrical conductivity of the hybrid composite is 150 S·m ^-1 or more, preferably 250 S·m ^-1 or more, more preferably 350 S·m ^-1 or more, still more preferably It may be 400 S·m ^-1 or more, more preferably 500 S·m ^-1 or more, and even more preferably 600 S·m ^-1 or more. In this case, the electrical conductivity of the hybrid composite may be measurable in the form of a polycrystalline pellet or a polycrystalline film. According to an embodiment of the present application, the electrical conductivity of the hybrid composite pellet is 150 S·m ^-1 or more, preferably 250 S·m ^-1 or more, more preferably 350 S·m ^-1 or more, more preferably It may be 400 S·m ^-1 or more, more preferably 500 S·m ^-1 or more, and even more preferably 600 S·m ^-1 or more. In addition, the electric conductivity of the hybrid composite film is 150 S·m ^-1 or more, preferably 250 S·m ^-1 or more, more preferably 350 S·m ^-1 or more based on an average film thickness of 500 nm. It may be preferably 400 S·m ^-1 or more, more preferably 500 S·m ^-1 or more, and even more preferably 600 S·m ^-1 or more.

That is, since the organic ligand of the metal-organic framework has pi-back bonding, it may have high electrical conductivity. On the other hand, the pi back bonding is a chemical concept in which electrons move from an atomic orbital of one atom to a π* anti-bonding orbital of another atom or ligand, specifically, by an aryl group included in an organic ligand. The bonding may be formed. In addition, since the hybrid composite of the present invention includes metal carbide having very high electrical conductivity (eg, Mxene 900 S/m ^-1 ), it can have very good electrical conductivity compared to the case of the metal-organic framework alone. there is.

In one embodiment of the present application, the hybrid composite may include a plurality of two-dimensional metal carbide sheets. At this time, the metal carbide sheet is titanium carbide, aluminum carbide, chromium carbide, zinc carbide, copper carbide, magnesium carbide, zirconium Zirconium carbide, molybdenum carbide, vanadium carbide, niobium carbide, iron carbide, manganese carbide, cobalt carbide, It may include metal carbide selected from the group consisting of nickel carbide, tantalum carbide, and combinations thereof, and may preferably include titanium carbide. At this time, the metal carbide sheet is specifically, first, by treating bulk metal carbide having a layered crystal structure in bulk form with HF, etc. to obtain expanded metal carbide in which each metal carbide layer is spread, and ultrasonic treatment (sonication) It may be manufactured by swelling (swelling) through and exfoliating (exfoliated) each metal carbide layer to obtain a metal carbide sheet.

In one embodiment of the present application, the metal-organic framework may be in a three-dimensional form depending on the type of organic ligand, but may also be in the form of a two-dimensional sheet. In this case, the metal-organic framework sheet has a thickness of 0.1 nm to 50 nm, preferably 1 to 30 nm, and may have an area of 1 nm ² to 100 μm ² , preferably 10 nm ² to 50 μm ² .

In one embodiment of the present application, the metal carbide sheet may have a thickness of 1 to 20 nm, preferably 5 to 15 nm, and an area of 100 nm ² to 100 μm ² , preferably 100 nm ² to 50 μm. It could be ² .

In one embodiment of the present application, the BET specific surface area of the crystalline lithium-metal oxide particles may be 20 m ² /g to 1200 m ² /g, preferably 30 m ² /g to 1000 m ² /g, More preferably, it may be 50 m ² /g to 950 m ² /g.

In one embodiment of the present application, the hybrid composite may have a porous structure, and specifically may include both micropores and mesopores. The total pore volume of the hybrid composite may be defined as the sum of the micro pore volume and the meso pore volume, and may further include other pore volumes. The total pore volume of the hybrid composite is 0.05 cm ³ /g or more, preferably 0.1 cm ³ /g or more, more preferably 0.25 cm ³ /g or more, still more preferably 0.3 cm ³ /g or more, even more preferably It may be preferably 0.4 cm ³ /g or more, 5.0 cm ³ /g or less, preferably 4.0 cm ³ /g or less, more preferably 3.0 cm ³ /g or less, and more preferably 2.0 cm ³ /g or less. , and more preferably 1.0 cm ³ /g or less. That is, since the hybrid composite has a high BET specific surface area and total pore volume, when the hybrid composite including the hybrid composite is used as an electrode active material for an electrochemical device such as a secondary battery or a supercapacitor, intercalation and deintercalation of electrolyte are easy, Electrochemical properties of the chemical element may be improved. That is, the hybrid composite includes both the unique porosity of the metal-organic framework (MOF) and the unique porosity of the metal carbide sheet, and the metal-organic framework (MOF) and the metal carbide sheet are randomly It may have a very high porosity because it also includes three-dimensional pores generated by mixing.

In one embodiment of the present application, the content of the metal oxide or metal carbide sheet relative to 100 parts by weight of the metal-organic framework may be 20 parts by weight to 70 parts by weight. If the content of the metal oxide or metal carbide sheet relative to 100 parts by weight of the metal-organic framework is less than 20 parts by weight, safety may decrease when used as an electrode, and if it exceeds 70 parts by weight, it is used as an electrode. Doing so may cause problems with capacity reduction.

The second aspect of the present application is,

mixing organic ligands and metal precursors; and mixing a two-dimensional metal carbide sheet with the mixture; It provides a method for preparing the hybrid complex, wherein the substituent included in the organic ligand forms a coordination bond with the metal precursor, respectively.

Although detailed descriptions of portions overlapping with those of the first aspect of the present application have been omitted, the contents described for the first aspect of the present application can be equally applied even if the description is omitted from the second aspect.

Hereinafter, a method for preparing a hybrid composite according to the second aspect of the present application will be described in detail.

First, in one embodiment of the present application, mixing the organic ligand and the metal precursor; includes.

In one embodiment of the present application, the organic ligand and the metal precursor may be mixed in a solvent. The solvent is water, methanol, ethanol, propanol, IPA (isopropyl alcohol), EG (Ethylene Glycol), ACN (Acetonitrile), EC (Ethylene carbonate), PC (Propylene carbonate), DMC (Dimethyl carbonate), DEC (Diethyl carbonate) ), EMC(Ethylmethyl carbonate), DME(1,2-dimethoxyethane), GBL(γ-butrolactone), MF(Methyl formate), MP(Methyl propionate), DMF(dimethylformamide), dimethyl sulfoxide(DMSO) , n-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), triethyl phosphate (TEP), and may include a material selected from the group consisting of combinations thereof.

In one embodiment of the present application, the metal precursor is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, selected from the group consisting of Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub and combinations thereof It may contain a precursor of a metal, preferably Ni. Meanwhile, the metal precursor may be provided in the form of a salt, and the salt may include chloride, fluoride, bromide, iodide, or triflate. , BF ₄ , PF ₆ , NO ^3- , SO ₄ ^2- , ClO ₄ ^- and combinations thereof.

In one embodiment of the present application, before the step of mixing the two-dimensional metal carbide sheet, ultrasonically dispersing the metal-organic framework in a solvent; may further include, the two-dimensional metal carbide sheet Prior to the mixing step, ultrasonically dispersing the two-dimensional metal carbide sheet in a solvent; may further include. Specifically, it refers to a process of exfoliating a two-dimensional metal-organic framework or the metal carbide in nano units using ultrasonic waves. In addition, non-limiting external force application means such as centrifugal separation may be further included to obtain the metal-organic framework and the metal carbide sheet peeled off as needed.

Next, in one embodiment of the present application, a step of mixing a two-dimensional metal carbide sheet with the mixture may be included, and substituents included in the organic ligand may form coordinate bonds with the metal precursor, respectively.

In one embodiment of the present application, the step of mixing the two-dimensional metal carbide sheet with the mixture may be characterized in that it proceeds by ultrasonic dispersion. Specifically, it may mean mixing the metal-organic framework and the two-dimensional metal carbide sheet by applying an external force to the mixture with ultrasonic waves. Ultrasonic dispersion may be performed for 30 minutes or more, preferably 45 minutes or more, more preferably 60 minutes or more, and 240 minutes or less, preferably 180 minutes or less, more preferably 120 minutes or less. there is. When the ultrasonic dispersion is performed for less than 30 minutes, dispersion or mixing may not be sufficiently performed, and when the ultrasonic dispersion is performed for more than 240 minutes, it may be uneconomical because sufficient mixing or dispersion has already been performed.

In one embodiment of the present application, mixing the two-dimensional metal carbide sheet to the mixture; Thereafter, a step of filtering through a filter may be further performed to obtain a powder of the hybrid composite. Vacuum filtration can be performed using, but not limited to, a PVDF membrane filter in a vacuum filtration device. At this time, the pore size of the filter is not limited as long as the hybrid composite can be filtered, and may be several nanometers or micrometers. Types of filters and filtration devices may also be used without limitation as long as those that can be commonly used.

In one embodiment of the present application, it is preferable to apply a heat treatment process to synthesize a metal-organic framework (MOF) precursor into a metal-organic framework and remove the solvent included in the mixture. The heat treatment may be characterized in that it is performed at a temperature of 40 ° C to 300 ° C, preferably 50 ° C to 250 ° C, more preferably 60 ° C to 200 ° C, and even more preferably 100 ° C to 180 ° C. In addition, the heat treatment may be characterized in that it is performed for 0.5 to 24 hours, preferably 1 to 12 hours, more preferably 1 to 5 hours.

In one embodiment of the present application, a metal-organic framework (MOF) precursor and a two-dimensional metal carbide sheet are mixed, and heat treatment is performed for a predetermined time to synthesize the metal-organic framework, and the two-dimensional metal carbide sheet and It is possible to form a hybrid complex by allowing the binding of to be performed simultaneously.

The third aspect of the present application,

It provides an electrode comprising the hybrid composite according to the first aspect of the present application.

Detailed descriptions of portions overlapping with the first and second aspects of the present application have been omitted, but the contents described for the first and second aspects of the present application can be equally applied even if the description is omitted in the third aspect. .

Hereinafter, an electrode including the hybrid composite according to the third aspect of the present application will be described in detail.

In one embodiment of the present application, the electrode may be used for secondary batteries or supercapacitors, and since the hybrid composite has high porosity and excellent electrical conductivity, energy density and output characteristics of the devices may be improved. there is. Specifically, the hybrid composite may have a total pore volume of 0.1 cm 3 /g to 1.0 cm 3 /g, and an electrical conductivity of 250 S·m ⁻¹ or more, and may be used as an active material for an electrode.

In one embodiment of the present application, the active material of the electrode may be formed on the electrode current collector. In this case, the type of the electrode current collector may not be significantly limited as long as it has conductivity without causing chemical change of the device. For example, the electrode current collector may include stainless steel, aluminum, nickel, titanium, calcined carbon, or a material in which carbon, nickel, titanium, silver, or the like is surface-treated on the surface of aluminum or stainless steel. Meanwhile, the electrode current collector may have a thickness of about 3 μm to 500 μm, and fine irregularities may be formed on the surface of the current collector to increase adhesion of the electrode active material. That is, it may be usable in various forms such as films, sheets, foils, nets, porous bodies, foams, and non-woven fabrics.

In one embodiment of the present application, the active material of the electrode may further include a conductive material and a binder in addition to the active material. In this case, the conductive material is used to impart conductivity to the electrode, and may be any material that has electrical conductivity without causing a chemical change in the device. For example, the conductive material is graphite such as natural graphite or artificial graphite, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, carbon-based materials such as carbon fiber, copper, nickel, aluminum , metal powder or metal fibers such as silver, conductive whiskey such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide or conductive polymers such as polyphenylene derivatives, and combinations thereof. it may be Meanwhile, the conductive material may be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the electrode active material.

In addition, the binder may serve to improve adhesion between particles of the electrode active material and adhesion between the electrode active material and the current collector. Specifically, the binder may be, for example, polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, Carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), alcohol It may include a material selected from the group consisting of phonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof and combinations thereof. Meanwhile, the binder may be typically used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the electrode active material.

In addition, the supercapacitor may preferably be a hybrid supercapacitor, and the hybrid supercapacitor may specifically include: an anode; cathode; It may include a separator and an electrolyte interposed between the positive electrode and the negative electrode. In this case, the electrode active material may be preferably used as an active material of the negative electrode, and activated carbon may be used as a positive electrode active material of the positive electrode.

In one embodiment of the present application, the electrolyte used in the hybrid supercapacitor may be a mixture of a salt and an additive in an organic solvent. At this time, the organic solvent is ACN (Acetonitrile), EC (Ethylene carbonate), PC (Propylene carbonate), DMC (Dimethyl carbonate), DEC (Diethyl carbonate), EMC (Ethylmethyl carbonate), DME (1,2-dimethoxyethane), It may include a material selected from the group consisting of γ-butrolactone (GBL), methyl formate (MF), methyl propionate (MP), and combinations thereof. In addition, the salt is used in an amount of 0.8 to 2 M, and may be a mixture of a lithium (Li) salt and a non-lithium salt. The lithium (Li) salt accompanies an intercalation/desorption reaction into the structure of the anode active material, that is, the hybrid composite, and its types include LiBF ₄ , LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiAlCl ₄ , LiCF ₃ SO ₃ , LiN It may include a material selected from the group consisting of (SO ₂ CF ₃ ) ₂ , LiC(SO ₂ CF ₃ ) ₃ , lithium bis(oxalato)borate (LiBOB), and combinations thereof. In addition, the non-lithium salt accompanies an adsorption/desorption reaction on the surface area of the carbon material additive, and may be used by mixing 0 to 0.5 M with the lithium salt. In this case, the non-lithium salt includes a material selected from the group consisting of TEABF ₄ (Tetraethylammonium tetrafluoroborate), TEMABF ₄ (Triethylmethylammonium tetrafluoroborate), SBPBF ₄ (spiro-(1,1′)-bipyrrolidium tetrafluoroborate), and combinations thereof it may be In addition, the carbon material additive may include a material selected from the group consisting of vinyl carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), and combinations thereof.

In one embodiment of the present application, the separator is positioned between the positive electrode and the negative electrode to prevent the positive electrode and the negative electrode from being in physical contact with each other and electrically shorted, and a porous material may be used. For example, the separator may include a material selected from the group consisting of polypropylene, polyethylene, polyolefin, and combinations thereof.

In one embodiment of the present application, the hybrid supercapacitor having the above configuration has high electrical conductivity because the hybrid composite is used as an anode active material, and the capacity is improved due to the high specific surface area of the carbon material additive, resulting in high energy density and output characteristics may have That is, a carbon material additive may be inserted into a plurality of spaces formed in the hybrid composite, and the hybrid supercapacitor including the additive may exhibit excellent electrical conductivity, capacitance, and output characteristics.

The fourth aspect of the present application,

It provides a catalyst comprising the hybrid composite according to the first aspect of the present application.

Detailed descriptions of portions overlapping with the first to third aspects of the present application have been omitted, but the contents described for the first to third aspects of the present application can be equally applied even if the description is omitted in the fourth aspect. .

The fifth aspect of the present application,

It provides an electromagnetic wave shielding material comprising the hybrid composite according to the first aspect of the present application.

Detailed descriptions of portions overlapping with the first to fourth aspects of the present application have been omitted, but the contents described for the first to fourth aspects of the present application can be equally applied even if the description is omitted in the fifth aspect. .

In one embodiment of the present application, the hybrid complex is a catalyst for water purification, an anticancer drug, an immunodeficiency virus treatment, a treatment for fungal and bacterial infection, a treatment for malaria, various drug delivery materials, a photocatalyst, a sensor, Since it can be applied in various fields such as aerospace materials, it can be used as a commercially very useful material. In addition, since it contains a metal carbide material having a Mxene structure, which is useful as an electromagnetic wave shielding material, application as an electromagnetic wave shielding material can be expected.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Preparation Example 1. Synthesis of metal carbide sheet

The high-purity Ti ₃ AlC ₂ powder was pulverized from the heat-treated sample, passed through a 400-mesh (38-μm) sieve, and then exfoliated using the HF etching process. The etching process is as follows. First, 1 g of LiF was dissolved in 10 mL of 9M HCl solution in a Teflon bottle with stirring; To the mixed etchant, 1 g of sieved Ti3AlC2 powder was slowly added, and the mixture was stirred at 40 °C for 24 hours. The suspension was then centrifuged, the supernatant was removed, and the precipitate was washed several times with deionized (DI) water until the pH approached neutral. Thereafter, the precipitate was dried in a vacuum oven to obtain Ti ₃ C ₂ T _x powder. 2 and 3 show SEM pictures of the surface of the synthesized metal carbide Ti ₃ C ₂ T _x sheet and low-magnification SEM pictures of the synthesized metal carbide Ti ₃ C ₂ T _x sheet, respectively.

Example 1. Preparation of hybrid composites

2,3,6,7,10,11-Hexaiminotriphenylene among substituted or unsubstituted C6 to C30 aryl-hexamine is used as an organic ligand, and two-dimensional electrical conductivity in which Ni is repeatedly bonded in a branched form A dispersion (metal-organic framework precursor) in which the Ni-organic structure was dispersed in a solvent was prepared. A SEM image of the surface of the synthesized metal-organic framework Ni ₃ (HITP) ₂ is shown in FIG. 4 .

A three-dimensional Ni ₃ (HITP) ₂ /MXene structure was prepared by exfoliating _sea urchin-shaped Ni ₃ (HITP) 2 and two-dimensional layered Ti ₃ C ₂ Tx using ultrasonic dispersion. 5 is a schematic view of manufacturing a Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x 3-dimensional composite.

The synthesized Ni ₃ (HITP) ₂ is dispersed in ethanol, which is a well-dispersible solvent, at a concentration of 1 mg/ml using a 300W ultrasonicator. Similarly, a Ti ₃ C ₂ T _x solution is prepared by using ultrasonic waves in ethanol or ethanol/water, which is a well-dispersible solvent. manufactured After slowly adding the Ti ₃ C ₂ T _x solution to the two Ni ₃ (HITP) ₂ solutions, they are dispersed using ultrasonic waves to prepare a final Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x solution. The prepared composite solution was vacuum filtered using a vacuum filtration device and a PVDF membrane filter (pore size: 0.22 micrometers), and the solvent was removed to obtain Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x MXene composite powder. 6 shows a method for preparing the Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x composite using an ultrasonic dispersion method and a vacuum filtration process.

Example 2. Preparation of hybrid composites

0.064 g Zn(NO ₃ ) ₂ ,6H ₂ O and 0.055 g 2-methyl imidazole were added to a 20 mL solution of Ti ₃ C ₂ T _x 20 mL exfoliated in formamide solution, and the respective concentrations were 16.8 mM and 33.6 mM. make it become Then, it was heated at 110° C. for one day in a Teflon reactor to obtain ZIF-8/Ti ₃ C ₂ T _x white powder. 7 briefly shows a method for synthesizing ZIF-8/Ti ₃ C ₂ T _x .

Experimental Example 1. SEM image of hybrid composite

The surface SEM picture of the synthesized Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x hybrid composite obtained above is shown in FIG. 8, and the cross-sectional SEM picture of the synthesized ZIF-8/Ti ₃ C ₂ T _x composite is shown in FIG. showed up

As shown in FIG. 8, it can be confirmed that the hybrid composite has a three-dimensional porous structure in which the existing aggregated Ni ₃ (HITP) ₂ structure is exfoliated and the sheet-type metal-organic skeleton and the metal carbide sheet are randomly mixed. could

In addition, referring to FIG. 9, it can be seen that the ZIF-8 fabricated on Ti3C2Tx in the form of a sheet has a layered structure, and the ZIF-8 is formed in a filled form inside the MXene sheet.

Experimental Example 2. BET result of hybrid composite

The specific surface area and pore distribution of each of the hybrid composite particles, metal-organic framework, and Mxene prepared in Example were measured and are shown in Table 1 and FIGS. 10 to 14 below.

Sample BET specific surface area
m ² /g firearms book
cm ³ /g Ni ₃ (HITP) ₂ 401 0.266 ZIF-8 1322 0.66 Ti ₃ C ₂ T _x 19 0.47 Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x 34 0.21 ZIF-8/Ti ₃ C ₂ T _x 918 0.636

As shown in Table 1, it can be seen that the hybrid composite according to the embodiment of the present invention has a relatively high BET specific surface area value compared to that of the parent material mexine, which can be seen as having a relatively high porosity.

Experimental Example 3. XRD analysis of the hybrid composite

XRD analysis was performed on the hybrid composite (Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x ) obtained in the above example, and the results are shown in FIG. 15 . Ni ₃ (HITP) ₂ , Ti ₃ C ₂ T _x , Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x Referring to FIG. 15 showing XRD results of each specimen, Ti ₃ C ₂ nanosheets in bulk form, respectively. The peak of was confirmed, and it was confirmed that it coincided with the theoretical peak. In addition, the peaks of the metal-organic framework (MOF) according to the above examples were confirmed, and it was also confirmed that each peak coincided with the theoretical peak.

Experimental Example 4. Electrochemical Characteristics Test

manufacture of electrodes

The synthesized Ni ₃ (HITP) ₂ , Ti ₃ C ₂ T _x or Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x was pulverized into powder of each specimen using a mortar or stirrer. Next, Super P, a conductive carbon, was added to the above powder in a ratio of 1:1 to 3:1 in a pestle bowl and mixed using a pestle. After mixing the well-mixed Ni ₃ (HITP) ₂ , Ti ₃ C _{2 Tx} or Ni ₃ (HITP) ₂ /MXene composite and Super P mixture with a PTFE binder in a weight ratio of 8:2, compress using a mortar and pestle. to prepare an electrode. The prepared electrode was formed to a thickness of about 150 μm using a roller.

Fabrication of evaluation cell

The electrode prepared as above is cut to a size corresponding to about 1 to 5 mg, and the cut electrode is used for secondary production using lithium foil, glass fiber separator, 1M LiPF ₆ EC/DMC electrolyte, and commercial 2032 coin cell parts. A battery coin cell was manufactured and the characteristics of the secondary battery were evaluated using electrochemical measurement and evaluation equipment.

Assemble a lithium half-cell for electrochemical evaluation of the Ni ₃ (HITP) ₂ , Ti ₃ C ₂ T _x or Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x electrode prepared according to the embodiment. and obtained a charge/discharge curve of the initial cycle in the voltage range of 0.0 to 3.0 V (vs. Li ⁺ /Li) at a C-rate of 50 mA/g, which is shown in FIG. 16. At this time, the charge/discharge capacity was converted into the capacity by dividing the total weight of the electrode.

According to the evaluation results, each charge/discharge capacity of Ni ₃ (HITP) ₂ was 656/719 mAh g ^-1 , and Coulombic efficiency (CE) was 109%. In addition, the 10-time charge/discharge capacity was 499/466 mAh g ^{-1 ,} respectively, and the coulombic efficiency was 93%. When charging and discharging is performed more than 10 times, capacity and coulombic efficiency decrease.

In the case of Ti ₃ C ₂ T _x MXene, each charge/discharge capacity was 322/378 mAh g ^-1 , respectively, and Coulombic efficiency (CE) was 117%. In addition, the 10-time charge/discharge capacity was 289/273 mAh g ^{-1 ,} respectively, and the coulombic efficiency was 105%. In the case of MXene, the initial capacity is lower than that of Ni ₃ (HITP) ₂ , but it shows high stability and coulombic efficiency.

On the other hand, in the Ni ₃ (HITP) ₂ /Ti ₃ C ₂ T _x composite electrode, each charge/discharge capacity was 905/960 mAh g ^{-1 ,} respectively, and a Coulombic efficiency (CE) of 106% was exhibited. In addition, the 10-time charge/discharge capacity was 736/734 mAh g ^-1 , respectively, and showed a coulombic efficiency of 100%. It showed higher initial capacity than Ni ₃ (HITP) ₂ , and showed high stability and coulombic efficiency even after charging and discharging 10 times.

Therefore, the hybrid composite of the present invention shows higher stability and coulombic efficiency after initial capacity and 10 charge/discharge cycles than when MOF Ni ₃ (HITP) ₂ or metal carbide sheet Ti ₃ C ₂ T _x Mxene is used alone. It was confirmed that this was due to complex structural and electrochemical properties, including enhancement of electrical conductivity of Ni ₃ (HITP) ₂ due to the addition of MXene and enhancement of porosity by forming a complex with MOF.

Claims (18)

metal-organic frameworks (MOFs); and
two-dimensional metal carbide sheet;
including,
The metal-organic framework is Ni ₃ (HITP) ₂ having a structure represented by Chemical Formula 7 below,
The two-dimensional metal carbide sheet is a Ti ₃ C ₂ Tx Mexene (MXene) nanosheet,
The metal-organic skeleton and the two-dimensional metal carbide sheet are randomly mixed to have a three-dimensional porous structure,
The metal-organic framework and the two-dimensional metal carbide sheet are ultrasonically dispersed in a solvent before mixing, and then the metal-organic framework ultrasonic dispersion and the two-dimensional metal carbide sheet ultrasonic dispersion are mixed by ultrasonic dispersion. Complex:
[Formula 7]
MLM
(In Chemical Formula 7,
M is Ni;
L is an organic ligand and is hexaiminotriphenylene (HITP) in the structure of Formula 10 below.)
[Formula 10]

(In Formula 10,
X ₁ to X ₆ are each independently an amine group (NH ₂ ), a carboxy group (COOH) or a hydroxyl group (OH);
X ₁ and X ₂ are equal to each other, X ₃ and X ₄ are equal to each other, X ₅ and X ₆ are equal to each other,
X ₁ , X ₃ and X ₅ are the same as or different from each other;
Y ₁ to Y ₆ are each independently carbon or nitrogen.)
delete delete delete delete According to claim 1,
The hybrid composite, characterized in that the BET specific surface area of the hybrid composite is 30 m ² /g to 1000 m ² /g.
According to claim 1,
The metal carbide sheet has a thickness of 1 to 20 nm, and an area of 100 nm ² to 100 μm ² The hybrid composite.
According to claim 1,
The metal-organic framework 100 parts by weight of the metal carbide sheet content is 20 parts by weight to 70 parts by weight of the hybrid composite.
According to claim 1,
The hybrid composite, characterized in that the total pore volume of the hybrid composite is 0.1 cm3 / g to 1.0 cm3 / g.
According to claim 1,
Electrical conductivity of the hybrid composite is 250 S·m ^-1 or more hybrid composite.
mixing an organic ligand and a metal precursor to obtain a mixture; and
mixing a two-dimensional metal carbide sheet with the mixture;
Substituents included in the organic ligand form a coordination bond with the metal precursor, respectively,
The metal-organic framework (MOF) obtained by mixing the organic ligand and the metal precursor to obtain a mixture has a two-dimensional shape,
Prior to mixing the two-dimensional metal carbide sheet with the mixture, the metal-organic framework and the two-dimensional metal carbide sheet are ultrasonically dispersed in a solvent, respectively, to obtain a metal-organic framework ultrasonic dispersion liquid and a two-dimensional metal carbide sheet ultrasonic dispersion liquid. Further comprising the step of preparing;
The mixing of the two-dimensional metal carbide sheet with the mixture is carried out by ultrasonically dispersing the two ultrasonic dispersions, the method for producing a hybrid composite according to claim 1.
delete delete delete ◈Claim 15 was abandoned when the registration fee was paid.◈ According to claim 11,
The ultrasonic dispersion is characterized in that carried out for a time of 30 minutes to 240 minutes or less, a method for producing a hybrid composite.
An electrode comprising the hybrid composite of any one of claims 1 and 6 to 10.
A catalyst comprising the hybrid composite of any one of claims 1 and 6 to 10.
An electromagnetic wave shielding material comprising the hybrid composite of any one of claims 1 and 6 to 10.

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